Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
  • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
  • C09B62/507—Azo dyes
  • C09B62/51—Monoazo dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
  • C09B62/443—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being alternatively specified
  • C09B62/447—Azo dyes
  • C09B62/45—Monoazo dyes

Definitions

• the invention is in the technical field of water-soluble azo dyes which have fiber-reactive properties.
• Azo dyes containing a 1,3-diaminobenzene-4-sulfonic acid as a coupling component are already known from the Japanese patent publication Sho-45-10789 and the German patent application 19 11 427. However, these have certain shortcomings, particularly with regard to the fastness of dyeings produced with them.
• the formula radical D is preferably a phenylene radical which is unsubstituted or by 1 or 2 substituents from the group lower alkyl, such as ethyl and especially methyl, lower alkoxy, such as ethoxy and especially methoxy, and chlorine or is substituted by a bromine atom, or is preferably a naphthylene radical which is unsubstituted or substituted by one or two, preferably one, sulfo group.
• acyl radical for the formula R is preferably a lower alkanoyl group which can be substituted by chlorine, bromine, lower alkoxy, such as methoxy and ethoxy, phenoxy, phenyl, hydroxy, carboxy or sulfo, such as, for example, the formyl, acetyl, propionyl -, Chloroacetyl, chloropropionyl, butyryl, isobutyryl, phenylacetyl or phenoxyacetyl group, or is preferably a lower alkenoyl group which can be substituted by chlorine, bromine, carboxy or sulfo, such as the monoacyl radical of maleic acid, the acryloyl radical or the ⁇ -bromoacryloyl radical, or is preferably a lower alkylsulfonyl group which can be substituted by hydroxyl, sulfato, chlorine, bromine or lower alkoxy, such as methoxy or
• formula member R is the acetyl, propionyl or benzoyl group.
• alkyl or alkylene or alkenyl radicals contained in the respective groups are those of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms.
• Alkaline eliminable groups Z are, for example, halogen atoms, such as the chlorine, bromine or fluorine atom, ester groups of organic carboxylic and sulfonic acids, such as a lower alkanoyloxy radical, for example the acetoxy radical, or an acyloxy radical of an aromatic carbon or sulfonic acid, such as the benzoyloxy, sulfobenzoyloxy -, Benzenesulfonyloxy or toluenesulfonyloxy, furthermore, for example, the monoester groups of phosphoric acid or in particular sulfuric acid or thiosulfuric acid corresponding to the formulas -OPO 3 M 2 or -OS0 3 M or -S-S0 3 M with M each having the meaning given above , also the lower alkylsulfonylamino and arylsulfonylamino groups, the phenoxy group, the dialkylamino groups with alkyl groups of
• the new azo compounds can be in the form of the free acid or in the form of their salts. They are preferred in the form of the salts, in particular the alkali and alkaline earth metal salts, of which in particular the sodium, potassium and also calcium salts.
• the new azo compounds are preferably used in the form of these salts, preferably the alkali metal salts, for dyeing and printing from Materials containing hydroxyl or carbonamide groups, in particular fiber materials.
• Y is preferably the vinyl group or the ⁇ -sulfatoethyl group
• R is the acetyl or propionyl group
• D is a.
• phenylene which may be substituted by one or two substituents selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chlorine and bromine, or the naphthylene radical which is unsubstituted or substituted by a sulfo group.
• the present invention further relates to processes for the preparation of the above-mentioned and defined azo compounds of the general formula (1).
• These compounds can be prepared according to the invention by using a compound of the general formula (2) in which D, n and Y have the meanings given above, diazotized and with a coupling component of the general formula (3)
• R and M have the meanings given above, couples to an azo compound of the general formula (1) and, if appropriate, in the case where Y stands for the ⁇ -hydroxyethyl group, the azo compound of the formula (1) with this ⁇ -hydroxyethyl group With the aid of a sulfating agent in the corresponding azo compound of the formula (1) in which Y represents the ⁇ -sulfatoethyl group, or with a phosphating agent in the corresponding compound of formula (1) in which Y represents the ⁇ -phosphatoethyl group , transferred.
• Suitable sulfating agents are, for example, 90 to 100% sulfuric acid, chlorosulfonic acid, amidosulfonic acid or other compounds which donate sulfur trioxide.
• Suitable phosphating agents are, for example, concentrated phosphoric acid, pyro-, meta- or polyphosphoric acid, polyphosphoric acid alkyl esters, phosphorus oxychloride or mixtures of phosphoric acid and phosphorus (V) oxide.
• the compounds of the general formula (3) which serve as coupling components for the synthesis of the compounds of the general formula (1) can also be prepared in a known manner, for example by monoacylation of 1,3-diamino-benzene-4-sulfonic acid with a corresponding acid chloride or acid anhydride of the formula radical R.
• Compounds of the general formula (3) are, for example: 3-amino-acetanilide-4-sulfonic acid, 3-amino-chloroacetanilide-4-sulfonic acid, 3-amino-propionylamino-benzene-4-sulfonic acid, 3-amino- ⁇ -chloropropionylamino -benzene-4-sulfonic acid, 3-amino-ß-sulfopropionylamino-benzene-4-sulfonic acid, 3-amino-acryloyl-amino-benzene-4-sulfonic acid, 3-amino-isobutyrylamino-benzene-4-sulfonic acid, 3-amino ⁇ -bromoacryloylamino-benzene-4-sulfonic acid, 3-amino-phenylacetylamino-benzene-4-sulfonic acid, 3-amino-methoxyacetylamino-benzene
• the diazotization of the amines of the general formula (2) can be carried out by generally known methods, for example by a effect of alkali nitrite and an inorganic acid, such as hydrochloric acid, sulfuric acid or phosphoric acid, or by nitrosyl sulfuric acid.
• the coupling with the coupling components of the formula (3) can also be carried out in a manner known per se in a neutral to acidic environment, preferably in a pH range between 1 *) and at a temperature between -5 ° C ' and + 25 ° C, if appropriate in the presence of sodium acetate or similar buffer substances or catalysts which influence the coupling rate, such as, for example, dimethylformamide or pyridine. * ) and 5, preferably between 2.5 and 4,
• the compounds of the formula (1) prepared according to the invention can be salted out by means of electrolytes, for example sodium chloride or potassium chloride, advantageously after the reaction mixture has been adjusted to a pH of 3.5 to 7 , 0, are separated from the reaction solution; after filtration they are dried.
• the compounds according to the invention can be isolated from their synthesis batches by evaporation or spray drying. It is also possible to feed the solutions of the compounds of the formula (1) obtained after the synthesis, if appropriate after adding buffer substances, directly as a liquid preparation for dyeing.
• the new compounds of formula (1) are suitable as dyes, in particular as fiber-reactive dyes; they can preferably be applied to the substrates mentioned below using the application methods known for reactive dyes and can be fixed in place.
• the present invention thus also relates to the use of the compounds of the formula .. (1) as dyes for dyeing and printing the materials mentioned at the beginning, in particular of materials made of cellulose fibers and / or natural and / or synthetic polyamide fibers or of leather or a process for dyeing and printing said materials, such as cellulose fiber materials or natural or synthetic polyamide fiber materials or of leather, using the compounds of the formula (1 ).
• materials such as cellulose fiber materials, cotton and regenerated cellulose, such as viscose silk, as well as linen, hemp ' and jute are preferred.
• Suitable polyamide fiber materials are in particular wool and other animal hair and silk, and of the synthetic polyamides in particular polyamide-6,6, polyamide-6, polyamide-11 or polyamide-4.
• azo compounds according to the invention on cellulose fibers by the exhaust process using a wide variety of alkali additives, dyeings with a very good color yield are obtained. With likewise excellent color yields, they dye cellulose fibers according to the known padding process, it being possible to fix the compound (1) by means of alkali by staying at room temperature, by steaming or with dry heat.
• the usual single-phase processes in the presence of an acid-binding agent or alkali-donating agent such as, for example, sodium bicarbonate, sodium carbonate or sodium trichloroacetate
• an acid-binding agent or alkali-donating agent such as, for example, sodium bicarbonate, sodium carbonate or sodium trichloroacetate
• the two-phase processes neutral or weakly acidic printing pastes after the printing of which the fiber material is either passed through a hot electrolyte-containing alkaline bath or padded with an alkaline electrolyte-containing pad liquor and the dye of the formula (1) is then fixed by steaming or dry heat.
• the compounds according to the invention are distinguished from the constitutionally closest comparable dyes of the Japanese patent publication Sho-45-10789 and DE-OS 19 11 427 by clearer nuances, considerably better light and acid fastness, better sweat and acidic overdye fastness; their nuances are just as insensitive to the crease-resistant finishing of the dyed or printed fabric.
• the dyeings or prints on cellulose fiber materials obtained with the compounds of the formula (1) have remarkable fastness properties; Of these, the most important manufacturing and usage fastnesses are to be emphasized, such as the light fastness on damp and dry fiber material, the fastness to washing at 60 ° C and 95 ° C, the fastness to soda • cooking, the acid and alkaline whale fastness, the fastness to water, the fastness to sea water, the acid fastness to over-dyeing, alkaline and acid fastness to perspiration, pleating, ironing and rubbing fastness as well as chlorine bath water and exhaust gas fastness. Copper salts do not change the nuance of the colors and prints even in the presence of detergents containing peroxide. The nuance is also not changed by synthetic resin equipment.
• Both the natural and the synthetic polyamide fiber materials are preferably dyed with the new compounds of the formula (1) from an acidic, aqueous dyebath or an acidic, aqueous dyebath.
• the desired pH of the dyebath or the dyebath is preferably adjusted with acetic acid or acetic acid and ammonium acetate or sodium acetate.
• leveling aids for example compounds based on a reaction product of a fatty amine, such as for example stearylamine, with an alkylene oxide, such as ethylene oxide, or a reaction product of cyanuric chloride with about 3 times the molar amount of an aminobenzenesulfonic acid and / or an aminonaphthalenesulfonic acid, in the dyebath or in the dyebath.
• the dyeings can usually be carried out at temperatures from 60 to 100 ° C., preferably in the exhaust process, in particular at the boiling point of the dye bath, or else in a pressure dyeing machine at temperatures from about 110 to 120 ° C.
• an aqueous solution of 23 parts of 3-amino-acetanilide-4-sulfonic acid is added and the pH is adjusted to about 4 by gradually adding sodium bicarbonate.
• the pH is adjusted to 5.5 to 6.0 and the azo compound formed is isolated by spray drying the aqueous solution.
• a yellow-orange, electrolyte-containing powder is obtained, which is the sodium salt of the compound of the formula contains.
• This has very good dye properties and is very suitable for dyeing (including printing) cellulose fibers such as cotton, for example, by the application and fixing methods customary for fiber-reactive dyes; it delivers clear, golden yellow dyeings and prints with good light and wet fastness properties.
• Good dyeings and prints are also obtained on wool, which are characterized by clear, golden yellow shades of high color strength and very good light and wet fastness properties.
• Example 1 The procedure described in Example 1 for the preparation of an azo compound according to the invention is followed, but instead of the coupling component used there, 24.4 parts of 3-amino-propionylamino-benzene-4-sulfonic acid are used. After working up the synthesis batch, the sodium salt of the compound of the formula is obtained which is also a valuable dye with fiber-reactive properties.
• This compound according to the invention dyes cellulose fiber materials according to the customary application and fixing methods for fiber-reactive dyes, likewise in clear, golden-yellow shades with good light and wet fastness properties. It also provides strong, level dyeings on wool with a clear, golden yellow shade and very good light and wet fastness properties.
• a solution of 23 parts of 3-amino-acetanilide-4-sulfonic acid is approximately used to carry out the coupling reaction 150 parts of water are added to the above diazonium salt solution, the pH being adjusted and maintained at about 4 using sodium bicarbonate. After coupling is complete, the pH is increased to 5.5 to 6 and the azo compound according to the invention precipitated by potassium chloride, suction filtered and dried at 60 ° C. under reduced pressure. (The azo compound can also be isolated by spray drying the aqueous solution).
• a gold-yellow, electrolyte-containing powder which contains the alkali metal salt, such as predominantly the potassium salt (or the sodium salt) of the formula contains.
• the compound according to the invention is outstandingly suitable as a dye and, according to the application and fixing methods customary and known for fiber-reactive dyes, gives cotton and wool clear, little reddish yellow dyeings and prints with very good fastness properties, which are mentioned in the description above.
• this diazonium salt suspension is added in small portions to an approximately 10 ° C. cold solution of 23 parts of 3-amino-acetanilide-4-sulfonic acid in 200 parts of water; the pH of the coupling solution is kept between 4 and 5 by sprinkling in sodium acetate.
• the coupling reaction is complete after about 2 hours.
• the azo compound according to the invention formed is isolated by spray drying.
• a brownish, electrolyte-containing powder is obtained, which is the sodium salt of the compound of the formula
• a red-brown, electrolyte-containing powder is obtained, which is the sodium salt of the compound of the formula contains, which is very suitable as a fiber-reactive dye for dyeing (including printing) cotton and wool; on these materials it delivers gold-orange dyeings and prints with good fastness properties.
• Example 1 The procedure of Example 1 is followed, except that the coupling component used there is replaced by 34.2 parts of 3-amino-p-tosylamino-benzene-4-sulfonic acid. After isolation, the sodium salt of the compound of the formula is obtained that provides dyeings and prints on cotton and wool with a strong reddish-yellow hue and good fastness properties.
• a neutralized solution of 41.1 parts of 2-amino-8- ( ⁇ -sulfatoethylsulfonyl) -naphthalene-6-sulfonic acid in about 250 parts of water is mixed with 20 parts by volume of an aqueous 5N sodium nitrite solution.
• This solution is slowly added to a mixture of 200 parts of ice and 35 parts of a 31% aqueous hydrochloric acid; the diazotization reaction is continued at about 10 ° C. with stirring for one hour. After completion, excess nitrous acid is destroyed in the usual way.
• Example 1 replaces the coupling component used there with 27.3 parts of 3-amino-N'-isopropylureido-benzene-4-sulfonic acid.
• a yellow-brown, electrolyte-containing powder is obtained, which is the sodium salt of the compound of the formula contains and that provides strong, golden orange dyeings and prints with good lightfastness and very good washfastness properties on cotton and wool according to the application methods customary for fiber-reactive dyes on cotton and wool.
• Example 2 The procedure of Example 2 is followed to produce an azo compound according to the invention, however, replaces the coupling component used there with 30.7 parts of 3-amino-N'-phenylureido-benzene-4-sulfonic acid.
• the alkali metal salt, such as sodium salt, of the compound of the formula is obtained which delivers strong, reddish-yellow dyeings and prints with good fastness properties according to the usual application techniques on cotton and wool.
• a brown-red, electrolyte-containing powder is obtained, which is the sodium salt of the compound of the formula contains.
• This likewise shows very good fiber-reactive dye properties and, according to the customary application techniques on cellulose fiber materials, gives yellowish orange dyeings with the good fastness properties mentioned in the description.
• the diazonium salt suspension thus prepared is mixed with a neutral aqueous solution of 32.2 parts of 3-amino-4-sulfo-phenylurea (which can be prepared from 18.8 parts of 1,3-diaminobenzene-4-sulfonic acid according to known procedures) 8.7 parts of potassium cyanate can be prepared at a pH of 5).
• the coupling mixture is stirred for a further 3 to 4 hours at a pH of 2.5 and the pH of the synthesis solution is adjusted to 4 to 6.
• the azo compound according to the invention is isolated by spray drying.
• a yellow-brown, electrolyte-containing powder is obtained which the alkali metal salt, predominantly sodium salt, of the compound of the formula contains, which has good fiber-reactive dye properties, a very good one
• azo compounds of the general formula (1) according to the invention characterized in the following table examples by their diazo components according to the general formula (2) and coupling components according to the general formula (3) can also be prepared in the manner according to the invention, for example according to the procedures of the above exemplary embodiments.
• azo compounds according to the invention likewise show very good fiber-reactive dye properties with very good application properties and provide dyeings and prints on the fiber materials mentioned in the description, in particular on cellulose fiber materials and wool, using the application and fixing methods customary for fiber-reactive dyes with good to very good fastness properties the specified colors on cotton.

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• 1981
  • 1981-08-31 DE DE19813134357 patent/DE3134357A1/de not_active Withdrawn
• 1982
  • 1982-08-24 IN IN979/CAL/82A patent/IN157076B/en unknown
  • 1982-08-26 EP EP82107846A patent/EP0073481B1/fr not_active Expired
  • 1982-08-26 DE DE8282107846T patent/DE3262152D1/de not_active Expired
  • 1982-08-30 AR AR82290474A patent/AR241199A1/es active
  • 1982-08-30 JP JP57149374A patent/JPS5842661A/ja active Granted
  • 1982-08-30 KR KR8203905A patent/KR890002350B1/ko active
  • 1982-08-30 BR BR8205080A patent/BR8205080A/pt not_active IP Right Cessation
  • 1982-08-31 CS CS826330A patent/CS233730B2/cs unknown
• 1986
  • 1986-10-30 US US06/926,803 patent/US4703112A/en not_active Expired - Lifetime

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